Derivatives of cycloaliphatic diamines as cosolvents for aqueous hydrophobic amines

ABSTRACT

The present invention relates to the use of cycloaliphatic diamines as cosolvents for hydrophobic amines in aqueous solution. The cycloaliphatic diamines of the present invention have a formula:  
                 
 
     where n is 1 or 2, each R is independently selected from a group consisting of: hydrogen, a 1 to 6 carbon aliphatic, and a 0 to 6 carbon containing amine, wherein each R is chosen such that the cosolvent amine comprises at least two amine groups; and a quantity of water to maintain said solution as a homogeneous phase. The cosolvent diamines have particular utility in the formation of water based epoxy resin curing agents. Superior water miscibility is achieved for hydrophobic amines through the use of cycloaliphatic amines as compared to conventional cosolvents.

FIELD OF THE INVENTION

[0001] This invention relates to solubilizing aqueous solutions ofhydrophobic amines with cycloaliphatic amine cosolvent, and moreparticularly to aqueous solutions of hydrophobic amines operative asepoxy resin curing agents which yield highly cross linked, waterresistant and abrasion resistant adhesive films.

BACKGROUND OF THE INVENTION

[0002] Epoxy resin curing agent systems were traditionally mixed in anorganic solvent base. Organic solvents have numerous problems includingflammability, cost and the polluting effects of volatile organiccomponent (VOC) release. Solvent recovery or vapor condensation aftercoating cure represent inefficient processes for coping with VOC releaseupon curing. Therefore, in order to comply with ever more stringentenvironmental regulations, there is a growing trend towards aqueousbased epoxy resin curing agents. As a result, there has beenconsiderable effort to develop water based epoxy resins and epoxy resincuring agents that upon mixing provide films having the same flexible,tough films obtained from solvent based mixtures.

[0003] The utilization of a surfactant to disperse hydrophobic epoxyresin curing agents in water have met with limited success. The filmsresulting from surfactant dispersions or emulsions generally exhibitedpoor chemical and water resistance, owing to the high concentration ofsurfactant contained within the films. Epoxy resin curing agents mostoften employed are amines such as polyamines or polyamides. Anotherapproach to obtain aqueous solutions utilized hydrophilic amines asepoxy resin curing agents. Such amines have an affinity for water thusobviating the need for surfactants; however, the resulting cured epoxyfilms demonstrate poor water resistance as compared to solvent basedfilms.

[0004] Superior epoxy resin curing agents, such as hydrophobic amineswhich form highly water resistant films, are not water soluble andrequire large quantities of cosolvent, surfactant or acid in order tocreate an aqueous dispersion or emulsion. This problem is exacerbatedwhen the epoxy resin curing agent is a high equivalent weight aminewhich tends to impart desirable flexibility on a resulting cured film.Prior art attempts to form aqueous solutions of hydrophobic amines haveutilized cosolvents including ethylene glycol ethers; polyoxyalkyleneamines, U.S. Pat. No. 5,250,109; butyl cellosolve, U.S. Pat. No.4,308,183; and the like which are described in U.S. Pat. No. 4,246,148;Bronsted and Lewis acids such as acetic acid and nitroparaffins.Unfortunately, cosolvents or acids tend to increase the concentration ofVOCs. Entrapment of cosolvents or acids furthermore tends to detractfrom film barrier properties and increase the water sensitivity of theresulting cured film. Commercially available hydrophilic amines serve asreactive cosolvents for the dissolution of hydrophobic amines in water.Dytek A (DuPont) and EDR 148 (Texaco) are examples of common hydrophilicamines. Unfortunately, such hydrophilic amines support only limitedaddition of water to a hydrophilic/hydrophobic amine blend prior tophase separation of the hydrophobic amine from the aqueous portion.

DESCRIPTION OF THE INVENTION

[0005] The present invention is directed towards aqueous solvents ofhydrophobic amines. While the description herein largely focuses onaqueous solutions of hydrophobic amines as epoxy curing agent systems,it is appreciated that solubilizing hydrophobic amines in water hasbroad applicability. For example, transmembrane proteins, dye compoundsand pharmaceuticals containing amine functionalities benefit fromaqueous solubilization according to the present invention.

[0006] The term “hydrophilic” as used herein defines a compound capableof forming the aqueous solution of a compound of a molarity greater than0.01 molar or in the case of a polymeric substance, forming a solutionat greater than about 5 parts by weight per hundred parts water.Consequently, the term “hydrophobic” defines a compound or polymericsubstance incapable of forming aqueous solutions of the aforementionedhydrophilic concentrations at room temperature.

[0007] The identity of the hydrophobic amine is dictated by parametersindependent of the present invention. For example, in the case of epoxyresin curing agents, the hydrophobic amine illustratively includesdiethylene triamine; di(aminoethyl)ether; polyfunctional amines;polyoxyalkylene polyamines such as polyoxyethylene-propylene polyamine;hydroxyethylamino ethylamine; ethylamino ethylamine; aldamine and thelike. The amine may also include a high equivalent weight mono orpolyamide having a similar aliphatic moiety as compared to thepolyamines, a polypeptide, or pharmaceutically active amine-containinghydrophobic compound.

[0008] The cosolvent diamines of the present invention aid insolubilizing the hydrophobic amine. The cosolvents of the presentinvention, alone or in combination, are characterized by being watermiscible and are satisfactory solvents for the hydrophobic amines. Thecosolvent diamines of the present invention are characterized by havingthe formula:

[0009] where n is 1 or 2 and the resulting cycloaliphatic is asubstituted cyclopentane or cyclohexane; where each R is independentlyhydrogen, a 1 to 6 carbon aliphatic, or a 0 to 6 carbon containingamine; where the various Rs are chosen such that the cosolvent aminecontains two or more amine groups. More preferably, the non-amine Rgroups independently each contain less than 3 carbon atoms. Still morepreferably, the amines are primary amines.

[0010] It is appreciated that the reactivity of a cosolvent amine as anepoxy resin curing agent and/or the salvation efficacy towards ahydrophobic amine is effected by steric effects associated withnon-hydrogen R groups. Ortho, non-hydrogen R groups exhibit the mostsignificant steric hindrance as compared to other isomers, yet theseother isomers are also operative herein.

[0011] In order to provide a biologically compatible carrier forpharmaceutical amines, it is appreciated that R is chosen to impartadditional moieties to a cosolvent diamine allowing for metabolicclearance and diminished toxicity. Such biologically clearable moietiesillustratively include hydroxyl, ketone, aldehydes, carboxylates,carbohydrates and the like.

[0012] A cosolvent diamine of the present invention is mixed with ahydrophobic amine of interest to form an amine blend. Thereafter, wateris added to the amine blend in any quantity prior to the formation of aturbid solution. Alternatively, the sequence of mixing the hydrophobicamine, cosolvent amine and water is altered to likewise obtain a clearsolution. The term “homogenous phase” as used herein refers to a liquidsolution which is clear as measured by visual inspection.

[0013] The ratio of cosolvent amine to hydrophobic amine is selectivelyvariable, dependent on characteristics including equivalent weight ofthe hydrophobic amine, miscibility limits of the cosolvent amine withwater at solution temperature, and desired hydrophobic amineconcentration in aqueous cosolvent solution. Preferably, the amine groupratio between the hydrophobic amine and cosolvent amine is from about0.5-5:1.

[0014] In the instance where the hydrophobic amine is an epoxy resincuring agent, the aqueous solution of the amine and cosolvent amine isutilized to prepare a dispersion of the epoxy resin. In general, it isconventional to employ the epoxy resin in an amount sufficient toachieve an epoxy to amine hydrogen equivalent weight ratio of from about0.5 to 1.5:1 and preferably from about 0.9 to 1.1:1.

[0015] The invention is additionally illustrated in connection with thefollowing examples which are to be considered as illustrative of thepresent invention. It should be understood that the invention is notlimited to the specific details of the examples, but rather to theappended claims.

EXAMPLE 1

[0016] 10 parts of a polyamidoamine (Air Products 506 amidoamine) isadded to a reactor equipped with a mechanical agitator. 10 parts of 1,3bis-aminomethylcyclohexane is added with stirring, 150 parts of roomtemperature water is added and the stirring continued until uniform,clear solution is formed. The solution is stable for greater than threemonths.

Example 2

[0017] To illustrate the efficiency of the present invention tosolubilize various hydrophobic amines, one part by weight of variouscommercially available hydrophobic amines is blended with one part byweight of a cosolvent amine. Water is then added dropwise with vigorousstirring to the blend of one part hydrophobic amine and one partcosolvent amine. The parts of water added is monitored by the appearanceof turbidity as measured by visible light scattering. The parts of wateradded to an amine blend that remains a clear solution is summarized forvarious cosolvents in Table 1. Cosolvents amines A-D are those of thepresent invention. In order to assess the relative efficiency of thecosolvent amines of the present invention, A-D; conventional cosolventamines, E-I and the omission of a cosolvent, J are also evaluated. Theresults are summarized in Table 1. TABLE 1 Parts of water added to 2parts of amine blend yielding a clear solution Air Products Air ProductsCardolite 2460 506 NC-540 Cosolvent Polyamide Amidoamine Phenalkamine A.Isophorone diamine >22 >28 >30 B. 1,3-Bis (aminomethyl) >10 >19 >18cyclohexane C. 1,2-Diamino 6 <6 <3.5 cyclohexane D. 1,2 Diaminocyclo- <5<5 <3.5 pentane E. Dytek A (DuPont) 3.5 <6 <3.9 F. 1,4-Bis(3- <2 <4 <.5aminopropyl) piperazine G. EDR 148 <2 <2 <.5 Texaco H. 1,2-Hexanediamine<3.6 <7 <3 I. m-Xylylenediamine <3.75 <5 <.5 J. None 0 <1 0

EXAMPLE 3

[0018] A lyophilized powder of bacteriorhodopsin is obtained accordingto D. Oesterhett Mtds. Enzy 31, 1974, 667. 0.1 gram of bacteriorhodopsinis mixed with 0.1 grams of 1,2 diaminocycylohexane cosolvent and 1.1grams of water added. The bacteriorhodopsin is uniformly dispersed inthe aqueous cosolvent as determined by small angle x-ray scattering.

EXAMPLE 4

[0019] An epoxy resin emulsion is prepared containing 55 parts Epon 828,40 parts water, 4 parts polyvinyl alcohol and 1 part Triton X-100.

[0020] The epoxy resin emulsion is mixed with 18 parts of an aqueousepoxy resin curing solution containing 14% by weight Air Products 2460polyamide and 9% by weight isophorone diamine. The resulting mixture isapplied to copper strips. Upon curing, a hard, clear water resistantfilm is obtained.

[0021] It is understood that the invention is not limited to thespecific descriptions above, which are intended to provide illustrative,working examples that encompass the inventive concept. Variousmodifications and changes which may be apparent to those skilled in theart to which the invention pertains may be made and also fall within thescope of the invention as defined by the following claims.

[0022] All patents and other publications cited herein are expresslyincorporated by reference.

1. An aqueous solution comprising: a hydrophobic amine; a cosolventamine of a formula:

where n is 1 or 2, each r is independently selected from a groupconsisting of: hydrogen, a 1 to 6 carbon aliphatic, and a 0 to 6 carboncontaining amine, wherein each R is chosen such that the cosolvent aminecomprises at least two amine groups; and a quantity of water to maintainsaid solution as a homogeneous phase.
 2. The solution of claim 1 whereinn is
 1. 3. The solution of claim 1 wherein n is
 2. 4. The solution ofclaim 1 wherein the at least two amines are primary amines.
 5. Thesolution of claim 1 wherein each R is independently selected from agroup consisting of: hydrogen, methyl, ethyl and 0 to 6 carboncontaining amine, wherein each R is chosen such that the cosolvent aminecomprises at least two amine groups.
 6. The solution of claim 1 whereinsaid cosolvent amine is isophorone diamine.
 7. The solution of claim 1wherein said cosolvent amine is a diaminocyclopentane.
 8. The solutionof claim 1 wherein said cosolvent amine is a bis-aminomethylcyclohexane.9. The solution of claim 1 wherein said cosolvent amine is a diaminecyclohexane.
 10. The solution of claim 1 wherein a ratio of saidhydrophobic amine to said cosolvent amine groups is from about 0.5 to5:1.
 11. The solution of claim 1 wherein a ratio of said hydrophobicamine to said cycloaliphatic amine groups is from about 0.8 to 2:1. 12.A method for forming an aqueous solution of a hydrophobic aminecomprising: mixing said hydrophobic amine with a cosolvent amine havingthe formula:

where n is 1 or 2, each R is independently selected from a groupconsisting of: hydrogen, a 1 to 6 carbon aliphatic, and a 0 to 6 carboncontaining amine, wherein each R is chosen such that the cosolvent aminecomprises at least two amine groups, and a quantity of water to maintainsaid solution as a homogeneous phase.
 13. The method of claim 12 whereinn is
 2. 14. The method of claim 12 wherein the at least two amines are aprimary amine.
 15. The method of claim 12 wherein each R isindependently selected from a group consisting of: hydrogen, methyl,ethyl and 0 to 6 carbon, wherein each R is chosen such that thecosolvent diamines comprise at least two amine groups.
 16. The method ofclaim 12 wherein said cosolvent amine is isophorone diamine.
 17. Themethod of claim 12 wherein said cosolvent amine is adiaminocyclopentane.
 18. The method of claim 12 wherein said cosolventamine is a bis-aminomethylcyclohexane.
 19. The method of claim 12wherein said cosolvent amine is a diamine cyclohexane.
 20. The method ofclaim 12 wherein a ratio of said hydrophobic amine to saidcycloaliphatic amine groups is from about 0.5 to 5:1.
 21. Use of acompound for solubilizing a hydrophobic amine in water, said compoundhaving a formula:

where n is 1 or 2, each R is independently selected from a groupconsisting of: hydrogen, a 1 to 6 carbon aliphatic, and a 0 to 6 carboncontaining amine, wherein each R is chosen such that the cosolvent aminecomprises at least two amine groups.